Silver halide material containing a monoazo dyestuff

ABSTRACT

Photographic light-sensitive material especially for the silver dyestuff bleaching process containing a monoazo dyestuff of the formula G-N=N-E(M-)m 1(NH-Y-Q)n 1NH-Z-A in which G is a naphthalene radical which in 1-position contains an azo group, in 2-position a phenylamino group and in 8-position a hydroxyl group and at least one sulfonic acid or sulfonic acid amide group, E is an aromatic radical which contains at most 2 sulfonic acid or sulfonic acid amide groups, M is a phthalic acid imide or an -NH-X-D- radical, X and Y are -CO- or -CO-NHradicals, D and Q are aromatic radicals, Z is an -SO2-, -CO- or CO-NH- radical, A is an aliphatic aromatic or heterocyclic radical and m and n are 1 or 2. These dyestuff are magenta dyestuffs and are fast to diffusion, easily soluble in water insensitive to calcium ions and completely bleachable to white.

United States Patent Piller [541 SILVER HALIDE MATERIAL CONTAINING AMONOAZO DYESTUFF [72] Inventor: Bernhard Piller, Marly-le-Petit,Switzerland [73] Assignee: Ciba Limited, Basel, Switzerland [22] Filed:Feb. 11, 1970 [21] Appl. No.: 10,602

[30] Foreign Application Priority Data Feb. 13, 1969 Switzerland..2163/69 [52] US. Cl ..96/99, 96/73, 96/20 [51] Int. Cl ..G03cl/10 58]Field of Search ..96/99, 73

[56] References Cited UNITED STATES PATENTS 3,21 1,554 10/1965 Dreyfuss..96/99 3,454,402 7/1969 Anderau et a1. ..96/99 [151 3,655,388 [4 1 Apr.11, 1972 Primary ExaminerJ. Travis Brown Attorney-Harry Goldsmith,Joseph G. Kolodny and Mario A.

Monaco [5 7] ABSTRACT Photographic light-sensitive material especiallyfor the silver dyestuff bleaching process containing a monoazo dyestuffof the formula in which G is a naphthalene radical which in l-positioncontains an azo group, in 2-position a phenylamino group and in8-position a hydroxyl group and at least one sulfonic acid or sulfonicacid amide group, B is an aromatic radical which contains at most 2sulfonic acid or sulfonic acid amide groups,

. M is a phthalic acid imide or an NHXD radical.

11 Claims, No Drawings The subject of the invention are monoazodyestufis of fordenote an optionally substituted benzene residue, A,denotes an optionally substituted lower aliphatic residue, an optionallysubstituted benzene residue or a heterocyclic residue containing N, O orS, m, n andp each denote 1 or 2, and X, Y and Z mula 5 have theindicated significance. l G N N E (M I Preferably, K, and K representsulphonic acid groups, and E, represents an optionally substitutedbenzene residue. To (N H Y Q N H Z A the extent that A, represents anoptionally substituted lower aliphatic residue, it is for example analkyl residue with at wherein (i denotes a naphthalene residue which inthe l- 10 most 4 carbon atoms, such as a methyl residue, or an aralkylposition contains an azo group, in the 2-position contains an residuesuch as an optionally further substituted benzyl optionally substitutedphenylamino group. and in the 8- residue. Amongst the heterocyclicresidues for A, 6-memposition contains a hydroxyl group, as well as atleast one bered N-heterocyclic residues and above all S-membered N,sulphonic acid or sulphonic acid amide group, E denotes O or especiallyS-heterocyclic residues are preferred. a mono or bicyclic aromaticresidue which contains at Special interest attaches to monoazo dyestuffsoffonnula OH R1 -N=N M2- m, (NH-YQ) l NH ZI AZ n,- IIIH 2 l most 2sulphonic acid groups or sulphonic acid amide groups, wherein L,represents a benzene residue which is substituted the residues 6 and Etogether contain 1 to 4 sulphonic acid at least once by a lower alkyl oralkoxy group, a halogen atom or sulphonic acid amide groups, M d n te ahth i gd orasulphonic acid, alkylsulphonyl or alkylcarbonyl group, R,imide residue bonded to E via the imide nitrogen atom or and R eachrepresent a hydrogen atom, a sulphonic acid denotes a residue of formulagroup or a lower alkyl group, and M, denotes a residue of for- (2) NHXD.mula which is bonded to E by the nitrogen atom, X and Y each NH-X denotea residue of formula CO which is bonded by the nitrogen atom to theresidue or R1 (3b) CO--NH,

with the nitrogen atom being bonded to D or O, D and Q denote a mono orbicyclic aromatic residue, Z denotes a residue of formula CO or CONl-l-,wherein the R2 nitrogen atom is bonded to A, or a SO residue, A denotesZ, denotes a residue of formula an aliphatic, aromatic or heterocyclicresidue, and 13 and n (3a) CO or (3b) CO NH each denote 1 or 2. E canfor example be an optionally further wherein the nitrogen atom is bondedto A A denotes a substituted naphthalene, diphenyl or above all benzenehydrogen atom, a lower alkyl group, a thienyl group or a residue.residue of formula At the same time monoazo dyestufis of formula (8) K.(Km-I112 H R O A Mr I V H Ra v 2 V H N=NE,(M1)m 1(NHYQr)n iNHZA1 whereinR, represents a hydrogen or halogen atom, an optionally substitutedlower alkyl or alkoxy group, an optionally NH substituted benzyl group,an optionally substituted benzoyl group, a phenylsulphonyl, nitro orcarboxyl group or an op- K dK h d t l h tionally substituted carboxylicacid amide group, and R and ale P E ld 1 an 5 i 6 a g R represent ahydrogen or halogen atom or a nitro, a lower Sulphomc acld i e g g em esalkyl or alkoxy group, and m, and n, are l or 2 and the sum of stuntedbenzene si fi 3 opnon i S if m, n, is at most 3, and X and Y have theindicated sigbenzene or naphth ene 1 enotes a res] o ornificance. Thelower alkyl or alkoxy residues for R,, R R,', mula NH X D R, and R orfor substituents in L, and A, as a rule contain at 1 (5) .most fourcarbon atoms, preferably one carbon atom. which is bonded to E, by thenitrogen atom, D, and Q, each Very suitable monoazo dyestuffs correspondto the formula HOgS wherein R denotes a hydrogen or chlorine atom or amethyl or methoxy group, R,, denotes a fluorine or chlorine atom or amethyl, methoxy, trifluoremethyl, methylcarbonyl, methylsulphonyl orsulphonic acid group and R denotes a hydrogen atom or a methyl group, Adenotes a hydrogen atom, an alkyl group with at most four carbon atomsor a residue of formula wherein R, denotes a hydrogen or chlorine atom,a methyl, methoxy, trifluoromethyl, nitro, phenylsulphonyl, or carboxylgroup, an optionally further substituted benzyl, benzoyl or carboxylicacid amide group, R denotes a hydrogen or chlorine atom, or a methoxy ornitro group, and M Y, 2,, m and n have the indicated significance.

Monoazo dyestuffs of formula wherein R R R Y, 2,, A and n, have theindicated significance, have proved particularly advantageous.

However, monoazo dyestuffs of formula Ho s are in turn particularlypreferred, wherein R denotes a methyl group or a chlorine atom, Rdenotes a chlorine atom or a methyl or methoxy group, and R denotes amethoxy group, or a chlorine or hydrogen atom. Such suitable dyestuffscorrespond to the formulae (26), (27), (30), (44), (51) and (55) quotedin the examples.

The dyestuffs of formulae (1), (4), (6), (9), (10), (1]) and (12) can bemanufactured according to various processes which are in themselvesknown. One process is for example characterized in that a compound offormula (13) G N N E (M---),,, (NH H 0-),( NH: is reacted with acompound of formula (14) A T wherein T denotes a residue of formula OCN,COHalor-SO l-Ial, with Hal representing a halogen atom, preferably achlorine atom, or with the anhydride of an aliphatic or aromaticmonocarboxylic or dicarbodylic acid, and G, E, M, Y, Q, A, m and nhaving the indicated significance.

An appropriate procedure for this is that, for example, an amine offormula z )-I-| 02 wherein E, M and m have the indicated significance isfirst diazotised and is coupled in an acid medium to a naphthylamine offormula (16) G H wherein G has the indicated significance. Thereafterthe nitro group is reduced in the usual manner. The aminomonoazodyestuff thus obtained is optionally reacted with a compound of formula1Q.N02 or (18) wherein E, M and m have the indicated significance and Wrepresents a residue of formula N W,,orNl-lW with W and W, eachrepresenting a removable protective group, with a compound of formula(16) and, after removal of the protective group, with a compound offormula (17) or l8) The condensation of amines with acid halides,isocyanates and anhydrides takes place according to methods which are inthemselves known and is advantageously carried out in a polar solventsuch as water or in a polar organic solvent such as pyridine, methanol,glycol, diethylacetamide, dimethylformamide or N methylpyrrolidone.

It can also be of advantage if the condensation is carried out in thepresence of acid-binding agents, such as for example alkali carbonates.Solvents such as pyridine or especially N- methylpyrrolidone inthemselves already act as acid-binding agents.

The residue G in formula (1) are derived from compounds of formula (16),which for example correspond to the following formulae:

CH; CH:

(16.25) Hols (16.26) Hols v OH E,

-OOCH; 0121 -OH OH 1 1 m NH m-CH: I l

l 01 COOH (1m) NH-O C-N o:

l V S OaH HzN- NHC ON H- NO:

I S 03H H2N NHC 0 CH1 I S 03H 1 HzN- I I s 03H l COOH HgN I N 01 l COOH,7 V S QgQHs The residues of formulae DXNH-andQ-YNH in formula (1) arefor example derived from the following acids or their halides, thefollowing isocyanates or the following anhydridcs: 3-nitrobenzoic acid,4-nitrobenzoic acid, 3- methyl-4-nitrobenzoic acid,3-methoxy-4-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid,2-chloro'5-nitrobenzoic acid, 4- chloro-3-nitrobenzoic acid,S-acetylamino-S-nitrobenzoic acid, 3-nitrophenylisocyanate,4-nitrophenylisocyanate, 4- nitro-l-naphthoic acid, 3-nitro-phthalicanhydride and 4- nitro-phthalic anhydride,

As examples of compounds of formula (14) from which the residues -z-aare derived there may be mentioned: acetic acid, trichloracetic acid,benzoic acid, 3-methylbenzoic acid, 4- methylbenzoic acid,4-methoxybenzoic acid, 4-phenoxybenzoic acid, 4-benzoylbenzoic acid,4-benzenesulphonylbenzoic acid, 3-chlorobenzoic acid, 4-fluorobenzoicacid, 3- acetylaminobenzoic acid, 4-acetylaminobenzoic acid, 4-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,4- dichlorobenzoicacid, 3-trifluoromethylbenzoic acid, 3- sulphobenzoic acid,3-sulphamidobenzoic acid, terephthalic acid, thiophene-Z-carboxylicacid, pyridine-4-carboxylic acid, furane-2-carboxylic acid,phenylisocyanate, 3-chlorophenylisocyanate, 4-chlorophenylisocyanate,4-methoxyphenylisocyanate, 4-trifluoromethylphenylisocyanate,4-nitrophenylisocyanate, 3-nitrophenylisocyanate,3,4-dichlorophenylisocyanate, 2,5-dichlorophenylisocyanate,4-acetylaminophenylisocyanate, 2,5-dimethoxyphenylisocyanate,Z-phenoxy-S- chlorophenylisocyanate and d-rnethylbenzenesulphonic acid.

The residues Z A can furthermore be derived from the followinganhydrides: acetic anhydride, maleic anhydride, benzoic anhydride,phthalic anhydride and 4-nitrophthalic anhydride.

The dyestuffs of formula (1) can be used for various purposes, forexample in photographic materials and herein particularly advantageouslyas image dyestuffs for the silver dyestufi bleaching process.Accordingly, valuable photographic materials can be manufactured in ausual manner which is in itself known, which contain at least one layerwith a dyestuff of formula (1) on a layer support.

In particular, these dyestuffs can be present in a multi-layer materialwhich contains, on a layer support, a layer dyed with green-bluedyestuff which is selectively sensitive to red, on top of this a layerdyed purple with a dyestuff of formula l) which is selectively sensitiveto green, and finally a layer dyed with a yellow dyestufi' which issensitive to blue. it is however also possible to incorporate thedyestuffs of formula (1) into an auxiliary layer or especially into alayer adjacent to the lightsensitive layer.

The dyestufi's of formula (1) simultaneously possess excellentdiffusion-resistance, but are at the same time also easily soluble inwater, insensitive to calcium ions and completely bleachable to white.

Compared to dyestufi's with an unsubstituted or alkyl-substituted aminogroup in the 2-position of the residue G, they are especiallydistinguished by better resistance to oxidizing baths, such as are forexample used in photographic reversal processes, and also by betterdiffusion resistance.

The dyestuffs according to the invention also offer numerouspossibilities for varying the spectral properties and are distinguishedby extraordinarily pure and brilliant color shades and by surprisinglyhigh color strength.

The extremely favorable shape of the spectral absorption curve permitsthese purple dyestuffs to be combined in many ways with one suitableyellow dyestuff and one suitable blue green dyestufi'. Grey shades whichappear neutral to the eye are thereby achieved over the entire densityrange.

EXAMPLE 1 21.6 g. of the arninomonoazo dyestuff of formula H03 S aredissolved in 400 ml. of water with the addition of the requisite amountof sodium carbonate, a solution of 14.8 g. of p-nitrobenzoyl chloride in20 ml. of acetone is added at pH 7 and room temperature whilst stirring,this addition is repeated after 2 hours, and the product which hasseparated out is filtered ofi.

is obtained in almost quantitative yield in the form of a winered powderwhich is a single substance according to a thin layer chromatogram.

21 g of nitro compound of formula (21), by reduction with sodiumsulphide, yields 12 g of pure amino compound of formula HO: S

The dyestuff of formula EXAMPLE 2 (21) 6.6 g. of amino compound offormula (22) are dissolved in H0 S 220 ml. of water to give a neutralsolution and are stirred at 3 y room temperature with repeated additionof a solution of 1.8 ml. of phenylisocyanate in 25 ml. of acetone untilno further starting product can be detected in the thin layerchromatogram.

4 A colourless by-product which has precipitated is filtered l OH 5 offand the dyestuff is precipitated with 7 N potassium acetate solution.The dark red powder which is obtained in almost H30 quantitative yieldcorresponds to formula (24) according to Table I. The dyestuffs offormula (25) to (69) are obtained analogously.

Absorption maximum in run In In DMF-HgO gela- Forrnula N0.GN=NE(M)m1(NH-YQ,)n-iNH- m n Z A (1:1) this (23) H03? 2 1 CO- i E522/538 563 OH NH IIIH H038 HJC CH3 (24) Sameasabove 2 1 CONH 522/637548 25) .do 2 1 CONH OCH3 524 550 Absorption maximum in 11111 In DMFJLIOgela- Formula No. GN=NE-(M-)m- (NHYQ)n- NH m 11 Z A (1: Line 26) .-do 21 GONH 530 55s 27) -410 2 1 CONH- -c1 522 530 (2a) .410 2 1 CONH -c1 53053s (29) .-do 2 1 CONH cm 530 540 (so) -do 2 1 -OONH -CH; 522 530 (31)do 2 1 -co @S0z 520 530 530 570 (32 "1103s 1 1 -CONH NH-- -0H l HOaS NHH=C CH3 524/538 524/546 (33) Sameasabove 1 1 --C0 CH2 N03 522/5311 550(34) "do 1 1 00 s02 (as 1 1 1 CONH NH- OH 1 1 CONH i 01 HO3S H3C@CH3(s7) Sameasabove 1 1 CONH -NO2 522/538 516 (as) H035 1 co N02 522/541524/545 NH- OH Q @1111 CH; 00 OH 1;:11 HOaS H30 F011,

(59) Sameasabove .V 2 1 -CONH Q (61) HOaS IFIH H Absorption maximum inrun In In DMF-H2O gela- Formula Nn. GN=N-E-(Mlm-x(NHYQ),,- NH- m n Z A(1:1) tine (67) HO |S 1 1 OO -CH3 524/536 531/548 I IP'H HOaS H30 -@-0CH3 (68) H035 1 1 C ONH Q01 535 548/587 0 H NH l I 171 H H038 @C O CH;

(69) 1 1 --C O -CH: 523 534 SOzCI-ls EXAMPLE 3 3.3 ml. of 6 percentstrength gelatine solution, 2.0 ml. of 1 percent strength aqueoussolution of the curing agent of for- 5 mula 0.5 ml. of a 1 percentstrength aqueous solution of the purple dyestufi' of formula (23) and3.3 ml. of silver bromide emulsion containing g. of silver per liter arepipetted into a test tube and made up to 10.0 ml. with deionized water.This solution is vigorously mixed and kept for 5 minutes at C. in awaterbath.

The casting solution, which is at 40 C., is cast onto a sub- 65 stratedglass plate of size 13 cm. X 18 cm. After solidifying at 10 C., theplate is dried in a drying cabinet with circulating air at 32 C.

A strip of this plate, cut to 3.5 cm. X 18 cm., is exposed to 500Lox/cm. for 24 seconds under a step wedge through a blue filter Kodak 2b49.

Thereafter the following procedure is adopted:

1. 7 minutes development in a bath which per liter contains g. ofanhydrous sodium sulphite, 12 g. of p-methyl-amino- 75 phenol sulphate,2 g. of sodium metaphosphate sll g of anhydrous potassium carbonate and10 g. of potassium bromide; 2. 2 minutes stop-fixing in a bath which perliter contains 15 g. of ammonium thiosulphate, 15 g. of potassiumaluminum 0 sulphate, 20 g. of sodium metaborate and 16 ml. of glacialacetic acid;

3. 2% minutes soaking;

4. 8 minutes color bleaching in a bath which per liter contains ml. of37 percent strength hydrochloric acid, g. of potassium bromide, 8 g. ofthiourea, 5 mg. of color bleaching catalyst of formula EXAMPLE 4 Thefollowing layers are successively applied to an opaque white acetatefilm provided with an adhesive layer:

1. Red-sensitive silver bromide emulsion in gelatine, containing thegreenish-blue dyestuff of formula EXAMPLE 5 A test strip manufacturedusing the purple dyestuff of formula according to Example 3, which hasbeen exposed, is processed as follows:

1. 5 minutes development in a bath which per liter contains 1 g. ofp-methylaminophenol sulphate, 20 g. of anhydrous sodium sulphite, 4 g.of hydroquinone, 10 g. of anhydrous sodium carbonate, 2 g. of potassiumbromide and 3 g. of sodi- 10 um thiocyanate;

2. 2 minutes soaking;

3. 2 minutes treatment in a reversal bath, which per litre contains 5 g.of potassium bichromate and 5 ml. of 96 percent strength sulphuric acid;

WWQ

2. Colorless gelatine layer without silver halide.

3. Green-sensitive silver bromide emulsion in gelatine, containing thepurple dyestuff of formula (23).

4. Blue-sensitive silver bromide emulsion in gelatine, containing theyellow dyestuff of formula (7 H0 3 H3C The gelatine layers can furthercontain additives such as wetting agents, hardeners and stabilisers forthe silver halide. In other respects, the procedure followed is that theindividual layers contain 0.5 g. of the particular dyestufi, and theamount of silver bromide corresponding to 1 1.2 g. of silver, per squaremeter of film.

This film is exposed to red, green and blue copying light under acoloured diapositive. Hereupon the copy is developed in accordance withthe following instruction:

1. 6 minutes development in a bath which per liter of water contains 50g. of anhydrous sodium sulphite, 0.2 g of lphenyl-3-pyrazolidone, 6 g.of hydroquinone, g. of anhydrous sodium carbonate, 4 g. of potassiumbromide and 0.3 g. of benztriazole;

2. 5 minutes soaking;

3. 6 minutes fixing in a solution of 200 g. of crystalline sodiumthiosulphate and 20 liter of water;

4. 5 minutes soaking;

5. 3 to 12 minutes color bleaching with a solution which per liter ofwater contains 50 to 80 g. of potassium bromide, to

g. of potassium metabisulphite in l 80 g. of thiourea, 35 to 80 g. of 30percent strength sulfuric acid and, if desired, 0.001 to 0.01 catalystof formula (71);

6. 10 minutes soaking;

7. 5 minutes bleaching of residual silver with a solution of g. of colorbleaching 60 g. of crystalline copper sulphate, 80 g. of potassiumbromide and 15 ml. of 30 liter of water;

8. 5 minutes soaking;

9. 5 minutes fixing as specified under 3.;

10. 5 minutes soaking.

A light-stable document-fast positive viewing image is obtained.

Similar results are obtained if instead of the dyestufi of forpercentstrength hydrochloric acid per mula (23) one of the dyestuffs offormulae (24) to (69) is 5 used.

4. 4 minutes soaking;

5. 5 minutes treatment in a bath which per liter contains 50 g. ofanhydrous sodium sulphite;

6. 3 minutes soaking;

7. 4 minutes development in a bath which per liter contains 2 g. ofl-phenyl-3-pyrazolidone, 50 g. of anhydrous sodium sulphite, 10 g. ofhydroquinone, 50 g. of anhydrous sodium carbonate, 2 g. of sodiumhexametaphosphate and 20 ml. of a 1 percent strength aqueous solution often-butylaminoborane;

8. 2 minutes soaking;

9. further treatment as specified in Example 3 under 4. to 10.

A brilliant, highly light-fast purple wedge running counter to theinitial original is obtained.

Similar results are obtained when using one of the dyestufis offormulas(23) to (24) or (26) to (69).

I claim:

1. A silver halide photographic light-sensitive material for the silverdyestuff bleaching process, which contains on a support, at least onelayer with a monoazo dyestuff of the formula G-N NE(M),,, ,(NHYQ)n-1NHZAin which G is a naphthalene radical which in the l-position contains anazo group, in the 2-position contains a phenylamino or phenylamino groupsubstituted by lower alkyl, lower alkoxy, halogen, sulfonic acid,alkylsulphonyl, alkylcarbonyl, phenoxy, carboxylic acid ortrifluoromethyl, and in the 8-position contains a hydroxyl group, aswell as at least one sulfonic acid or sulfonic acid amide group, E is aphcnylene, diphenylene or naphthalene radical which contains at most 2sulfonic acid or sulfonic acid amide groups, the radicals G and Etogether contain 1 to 4 sulfonic acid or sulfonic acid amide groups, Mis a phthalic acid imide radical bonded to E via the imide nitrogen atomor is a radical of the formula which is bonded to E by the nitrogenatom, X and Y each is a C0 or CO-NH radical, with the nitrogen atombeing bonded to D or Q, D and Q each stands for a phenylene, diphenyleneor naphthalene radical, Z is an SO --CO or CONH radical in which thenitrogen atom is bonded to A, A is an aliphatic, aromatic orheterocyclic radical, and m and n each is l or 2.

2. Photographic material according to claim 1, which conwhich is bondedby the nitrogen atom to the radical tains a dyestufi' of the formula 10NH k Z is a CO or C0Nl-lradical wherein the nitrogen a atom is bonded toA A is a hydrogen atom, a lower alkyl L group, a thienyl group or aradical of the formula in which K and K each is a sulfonic acid orsulfonic acid R amide group, L a benzene radical or benzene radical sub-1 stituted by lower alkyl, lower alkoxy, halogen, sulfonic acid,carboxylic acid, alkylsulphonyl, alkylcarbonyl, phenoxy or R,

trifluoromethyl, E is an unsubstituted benzene or 3 naphthalene radicalor a benzene or naphthalene radical substituted by sulphonic acid, loweralkyl, lower alkoxy, sulfonamide, N-methyl sulfonamide, methylsulfonylor carboxylic in which R, is a hydrogen or halogen atom, a lower alkyl,a acid M is an NH--XD, radical, which is bonded to E chlorinated loweralkyl, a lower alkoxy, a benzyl, a p-carboxyby the nitrogen atom, D andQ each is a benzene radical or a or p-nitro-benzyl, a benzoyl, ap-carboxybenzoyl, a phenylbenzene radical substituted by nitro, methyl,methoxy, sulfonyl, a nitro, a carboxyl, a carboxylic acid amid and R,acetylamino or chlorine, A, is a lower aliphatic radical, or a and Reach is a hydrogen or halogen atom, a nitro, a lower chlorinated loweraliphatic radical, a benzene radical, or 3 alkyl or a lower alkoxygroup, and m, and n, are 1 or 2 and the benzene radical substituted byhalogen, lower alkyl, lower alsum of m, n, is at most 3, and X and Yhave the significance koxy, benzyl, phenylsulphonyl, nitro, carboxyl,carboxylic indicated in claim 1. acid amide, trifluorornethyl, acetyl,acetylamino, sulfonic 4. Photographic material according to claim 3,which conacid, sulfonic acid amide, phenoxy, p-carboxy-benzoyl, ptainsadyestufi' of the formula -OH -N=N EM (NIIY) l NH-Z|A;

N H S 03H 7 R5 R;

nitro-benzyl or p-carboxy-benzyl, or a heterocyclic radical wherein Rdenotes a hydrogen or chlorine atom or a methyl containing N, O or S; m,n and p each is l or 2, and X, Y and Z or methoxy group, R denotes afluorine or chlorine atom or a have the significance indicated inclaim 1. methyl, methoxy, trifluoromethyl, methylcarbonyl, methylsul- 3.Photographic material according to claim 1, which confonyl or sulfonicacid group and R denotes a hydrogen atom tainsadyestufi of the formulaor a methyl group, A denotes a hydrogen atom, an alkyl i NH R;

in which L is a benzene radical which is substituted at least group withat most four carbon atoms or a radical of the foronce by a lower alkylor alkoxy group, a halogen atom or a sull fonic acid, alkylsulfonyl oralkylcarbonyl group, R and R each represents a hydrogen atom, a sulfonicacid group or a lower alkyl group, M is a radical of the formula whereinR, denotes a hydrogen or chlorine atom, a methyl, 11 s methoxy,trifluoromethyl, nitro, phenylsulfonyl, or carboxyl group, a benzoyl, ap-carboxy benzoyl, a carboxylic acid amide R is a hydrogen or chlorineatom, or a methoxy or nitro group, and M,, Y, 2,, m and n have thesignificance in- 5 dicated in claim 3.

5. Photographic material according to claim 4, which contains a dyestuffof the formula 111 use our 'R H 0 s 4 0n (NlIY N:N l 9. Photographicmaterial according to claim 1, which contains a dyestuff of the formulaI? I I S 0111 N HZiAa R3 n H O; S J Y O H N HO C- Ra XE &

in which R R R Y, 2,, A and 11 have the significance in- NH dicated inclaim 4 p 6. Photographic material according to claim 4, which con- INH- CONH tains a dyestufi of the formula 10. Photographic materialaccording to claim 1, which contains a dyestufi' of the formula in whichR denotes a hydrogen atom, a chlorine atom, a NH H0 8 trifluoromethyl,methyl, methoxy, phenylsulfonyl, carboxyl, NH C ONH-Qcl carboxybenzyl orp-carboxybenzoyl group, and R R R R HSC H; Y, Z, and n have thesignificance indicated in claim 4. I

7. Photographic material according to claim 1, which contains a dyestuffof the formula M H O 3 S ll. Photographic material according to claim 1,which con- OH NHC 0 tains a dyestuff of the formula v 1TH SOsH V/ 1103sCH3 OH NHOC NH c0 NH 5 in which R denotes a methyl group or a chlorineatom, R denotes a chlorine atom, a methyl or methoxy group, and Rdenotes a methoxy group or a chlorine or hydrogen atom.

8. Photographic material according to claim 1, which contains a dyestuffof the formula a s11: mun: m4

zg g UNITED STATES PATENT OFFICE CERTIFICATE OF CGRECTION Patent No.3,655 388 Dated April 11, 1972 Inventor (s) BERNHARD PILLER It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 1, [T3] Assi nee: Ciba Limited, Basel, Switzerland" should read73] Assignee: CIBA-GEIGY AG, Basel Switzerland Column 26, claim 1, line55 should be amended to read:

Column 27, claim 2, lines 5-13, the left-hand portion of the structuralformula should be amended to read:

'" K K H l 2 p-l 2-p Page 1 of 2 2 3 UNITED STATES PATENT OFFICE i vCERTIFICATE OF CORRECTION Patent No. 1655388 Dated A -i1 1972 Inventors) BERNHARD FILLER It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

j Column 30, claim 10, lines 39 to 50, the left-hand portion 0 thestructural formule should be amended to read:

"' HO s H C CH Signed and sealed this 8th day of May 1973.

(SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents Page 2 of 2

2. Photographic material according to claim 1, which contains a dyestuffof the formula
 3. Photographic material according to claim 1, whichcontains a dyestuff of the formula
 4. Photographic material according toclaim 3, which contains a dyestuff of the formula
 5. Photographicmaterial according to claim 4, which contains a dyestuff of the formula6. Photographic material according to claim 4, which contains a dyestuffof the formula
 7. Photographic material according to claim 1, whichcontains a dyestuff of the formula
 8. Photographic material according toclaim 1, which contains a dyestuff of the formula
 9. Photographicmaterial according to claim 1, which contains a dyestuff of the formula10. Photographic material according to claim 1, which contains adyestuff of the formula
 11. Photographic material according to claim 1,which contains a dyestuff of the formula